JP2009514177A5 - - Google Patents

Description

According to a further aspect of the invention,
A substrate;
A cover plate;
A blue light-emitting addressable electroluminescent pixel array disposed between the substrate and the cover plate;
A peripheral seal that contacts the substrate and extends from the substrate to the cover plate to prevent the electroluminescent pixel array from being exposed to air pollutants;
An optically clear double sealing structure comprising a lower planarizing polymer layer deposited and deposited on the pixel array and an upper inorganic sealing layer deposited on the lower polymer layer;
A photoluminescence color conversion layer attached to the double ceiling structure and arranged side by side in the sub-pixels of the pixel array to convert blue light from at least some of the pixels in the pixel array into visible light of a different color;
A sealed electroluminescent display comprising: an optically transparent inorganic sealing layer attached to the color conversion layer.

According to another aspect of the invention,
A substrate;
A cover plate;
An electroluminescent pixel array disposed between the substrate and the cover plate and comprising a thick film dielectric layer and a blue light emitting layer;
A peripheral seal that contacts the substrate and extends from the substrate to the cover plate to prevent the electroluminescent pixel array from being exposed to air pollutants;
A sealed electroluminescent display comprising: a multi-layer sealing structure on a display comprising alternating polymer layers and inorganic layers deposited on an underlying pixel array.

According to another aspect of the invention,
A substrate;
A thick dielectric layer type electroluminescent pixel array provided on the substrate;
A laminated seal structure in a display provided above the thick film dielectric layer type electroluminescent pixel array;
The seal structure includes a lower layer deposited on the upper conductor array of the display and an upper moisture-impermeable layer deposited on the lower layer, and the lower layer of the seal structure has an upper moisture impermeability of the seal structure. A sealed electric field that provides a means of absorbing or reacting to the vapor emanating from the pixel array to substantially prevent pressure buildup between the transmissive layer and the pixel array and avoid breaking the upper moisture impermeable layer. Luminescent display.

According to yet another aspect of the invention,
A substrate;
An electroluminescent pixel array provided on the substrate;
A lower layer deposited on the upper conductor array of the display; and a display sealing structure comprising an upper moisture-impermeable layer deposited on the lower layer;
The sealed electroluminescent display, wherein the lower layer of the seal structure provides a means for relieving mechanical stress between the moisture impermeable layer of the seal structure and the pixel array and avoiding breakage of the upper moisture impermeable layer.

According to another aspect of the present invention, there is provided a method for manufacturing a sealed electroluminescent display comprising a substrate and an electroluminescent pixel array comprising a laminated seal,
Deposit a liquid or slurry precursor layer adjacent to the top electrode array of the display and cure the deposited layer to form a polymer layer, thereby providing a smooth, substantially pinhole free thin film inorganic Allowing the layer to have a smooth upper surface to facilitate subsequent deposition of the layer;
Vacuum depositing an inorganic thin film substantially free of pinholes on the organic layer.
Depending on the embodiment, the liquid or slurry is a monomer-containing liquid or slurry. In other embodiments, the liquid or slurry precursor layer is deposited by applying a monomer-containing liquid or slurry adjacent to the top of the display electrode array.

According to another aspect of the present invention, there is provided a method for manufacturing a sealed electroluminescent display having a substrate and an electroluminescent pixel array comprising a laminated seal,
Depositing a precursor layer adjacent to the top electrode array of the display by condensing the vapor and curing the deposited layer to form a polymer layer, thereby providing a smooth, substantially pinhole free thin film inorganic Allowing the layer to have a smooth upper surface to facilitate subsequent deposition of the layer;
Vacuum depositing an inorganic thin film substantially free of pinholes on the organic layer.
According to an embodiment, the steam is a monomer containing steam.

According to another aspect of the invention is a method of manufacturing a sealed electroluminescent display having a substrate and an electroluminescent structure comprising a laminated seal as described herein in some embodiments,
Print a UV curable resin lacquer forming film adjacent to the top electrode and cure the printed formed film so that the film facilitates subsequent deposition of a smooth, substantially pinhole free thin film inorganic layer And having a smooth upper surface to do;
Vacuum depositing the inorganic layer on the polymer layer.

The polymer layer is planarized with a uniformly smooth and substantially pinhole-free top inorganic layer deposited thereon that serves as an effective barrier against humidity and other contaminants from the surrounding environment Provide a polished surface. The polymer layer and inorganic layer of the laminated seal are in direct contact with each other. The multi-layer structure of the laminated seal of the present invention retains the integrity that the display is manipulated by resistance to rupture when volatile species are generated from the display structure over time.

In another embodiment of the present invention, the polymer layer of the laminated seal functions as a color conversion function, functions as a stress release between the display structure and the moisture-impermeable inorganic layer, and deposits the moisture-impermeable inorganic layer. Multiple functions with two or more functions selected from the functions as a flattened surface and a function as a getter or absorber for vapors and gases generated inside the display during operation. A functional layer is provided. The surface of the polymer layer needs to be sufficiently smooth. This is to ensure that the thin film inorganic layer can be vacuum deposited on the top surface of the polymer layer so that it is substantially free of pinholes and other mechanical defects that act as a conduit for moisture transfer. is there.

The lower polymer layer is made of optically transparent urethane, polyamide, acrylate, polyimide, polybutylene, isobutylene, isobutylene isoprene, polyolefin, epoxy, parylene, benzocyclobutadiene, polynorbornane, polyaryl ether, polycarbonate, alkyd, polyaniline, ethylene From vinyl acetate and ethylene acrylic acid, polystyrene, polyester, silicone, polysilicone, polyphosphazene, polysilazane, polycarbosilane, polycarborane, carboranesiloxane, polysilane, phosphonitrile, sulfur nitride polymer, siloxane, and combinations thereof The material selected from the group. In an embodiment of the invention, the lower polymer layer is a color conversion layer as described in Applicant's PCT application CA2005 / 000756, the disclosure of which is incorporated herein by reference in its entirety. Also good. Briefly, such a color conversion layer is dispersed in an ultraviolet curable resin and comprises a fluorescent pigment particle composition. The fluorescent pigment particles comprise at least one dye and a polymer material (in one embodiment of the invention, a molecular additive such as an ultraviolet absorber (UVAs), a hindered amine light stabilizer (HALS) or a nickel compound) Is further added). UV absorbers (UVAs) are chosen to selectively absorb UV light and minimize blue light absorption without interfering with the ability of the photoinitiator used in the resin to be activated by UV light. . The fluorescent pigment particles are then mixed and dispersed throughout a transparent UV curing agent (eg, an acrylate melamine resin with a photoinitiator to pattern the paste). The color conversion layer is provided as a paste deposited as a uniform film and then patterned on the electroluminescent panel using a conventionally known photolithographic method. Usually, one color-converting photoluminescent layer is used for red and one layer is used for green, and the layer composition is different for red and green. The paste is deposited to form a homogeneous layer of a first color conversion photoluminescent layer (eg, green) on the subpixel array using techniques known to those skilled in the art, such as screen printing techniques. The subpixel array is as disclosed in Applicant's PCT application PCT CA03 / 01567, the disclosure of which is hereby incorporated by reference in its entirety. In order to activate the photoinitiator that cures the resin, the uniform screen printed film is exposed to UV light through a photomask having the desired pixel pattern, and then the desired pattern of the first color conversion photoluminescent layer is exposed. The portion that has not been exposed to ultraviolet light to produce is dissolved in a solvent (described in Applicant's PCT patent application PCT CA03 / 01567). This process is repeated for the second color conversion photoluminescence layer. After UV curing, the single layer or layers are subjected to thermal baking to remove monomers, residual photoinitiators, oligomers, and other volatile species by outward diffusion and evaporation. Thermal curing is performed at a temperature range of about 80 ° C. to about 160 ° C. (any range therebetween) for about 2 hours or more.

The thickness of the lower polymer layer, which can also be a color conversion layer, is determined based on the light absorption characteristics of the layer. The thickness of the polymer layer is selected based on the thickness required to obtain a sufficiently smooth surface to deposit a pinhole free inorganic layer. As will be discussed below, when getters are incorporated into a polymer layer, as will be understood as one technique in the art, from display structures that need to be absorbed during display operation. Based on the predicted amount of gas generated, the thickness is sufficient to include an appropriate amount of getter. If the polymer layer and the color conversion layer are the same layer, the required thicknesses must be compatible and such requirements are readily determined by those skilled in the art.

The laminated seals of the present invention are typically used for thick film dielectric electroluminescent displays constructed on glass, glass ceramic, ceramic or other heat resistant substrates. In the display manufacturing process, a set of lower electrodes must first be deposited on a substrate. Additionally, a thick film dielectric layer is deposited using the thick film deposition technique illustrated in US Pat. No. 6,771,019, the disclosure of which is incorporated herein in its entirety. This thick film layer typically comprises a sintered perovskite piezoelectric material or a ferroelectric material such as lead magnesium niobate (PMN) or lead magnesium titanium zirconate having a dielectric constant of several thousand. On top of this thick film, using a metal organic deposition (MOD) or sol-gel method to deposit a thin film light emitting structure with a smooth surface, a compatible piezoelectric or strong material such as lead zirconate titanate, for example. A thin coating layer (smooth layer) of a dielectric material may be formed. Applicant's US Pat. No. 5,432,015, the disclosure of which is incorporated herein by reference in its entirety, discloses a thick film dielectric layer composite structure for use in electroluminescent displays. Yes. The thick dielectric layer may be further mechanically compressed as described in Applicant's PCT patent application WO 00/70917. In addition, Applicant's international patent application PCT CA02 / 01932 (the disclosure of which is incorporated herein by reference in its entirety) is a variation of a thick film paste formation method used to form a thick film dielectric layer. Is disclosed. The thick film dielectric layer formed by this method may be sintered at a low temperature of 650 ° C. to facilitate the use of the glass substrate, and can be used as a thick film dielectric in the present invention.

Then, on the thick dielectric layer, as described in Applicant's US Pat. No. 6,589,674, the disclosure of which is incorporated herein in its entirety. Depositing a thin film structure comprising more thin film dielectric layers (eg, made of barium titanate sandwiching one or more thin light emitting films between them) followed by U.S. Patent Application Publication No. 0013906 Pat (the disclosure of which is incorporated in its entirety herein) depositing a light transmissive of a set of upper electrode by using a vacuum technology that is illustrated in. Another embodiment of a full color thick film dielectric layer electroluminescent display is illustrated by US Patent Application Publication No. 2004/0135495, the disclosure of which is incorporated herein in its entirety. In this embodiment, the red, green, and blue subpixels comprise blue emitting electroluminescent elements. This blue light-emitting electroluminescent element directly acts as a light source of the blue sub-pixel, covers the blue light-emitting element, and activates the red and green photoluminescence color conversion layers activated by the blue light-emitting element, Red and green sub-pixels emit light.

In FIG. 1A, a part of the sub-pixel structure of the electroluminescent display is indicated by reference numeral 10. The electroluminescent display 10 comprises a substrate 20, a cover plate 22, an electroluminescent display structure 24 between the two, an electroluminescent display structure 24 (blue light-emitting addressable electric field) from the substrate 20 and one or more air pollutants. There is an optional peripheral seal (not shown) between the cover plate 22 for protecting the light-emitting pixel array). The peripheral seal extends to and contacts the cover plate 22 and the substrate 20 and fills the entire gap between the cover plate 22 and the substrate 20 only on the outer periphery of the display. The peripheral seal does not contact the electroluminescent display structure 24. Details are described in Applicant's co-pending US patent application serial number 10 / 885,257, the disclosure of which is incorporated herein by reference in its entirety. Substrate 20 has a lower electrode 30 thereon, followed by a thick film dielectric layer 32, a dielectric smoothing layer 34, and an optional thin film dielectric layer 36 made of a material such as barium titanate thereon. . The blue light emitting layer 38 is provided on the thin film dielectric layer where the upper thin film dielectric layer 40 is shown, and is made of a material such as aluminum nitride. Three subpixel columns 42, 44 and 46 are disposed on the upper thin film dielectric layer 40. These subpixel columns facilitate application of a voltage for causing the light emitting layer to emit light. The upper thin film dielectric layer 40 separates the subpixel columns 42, 44, 46 from the light emitting layer 38. The subpixel column 42 has a green conversion layer 48 above it. Similarly, the subpixel column 44 has a red color conversion layer 50 thereabove. The subpixel column 46 corresponding to the blue subpixel does not have a color conversion layer, but has a light transmission layer 55 having a refractive index selected to minimize reflection of light between layers. The cover plate 22 is placed over the entire substrate facing the deposited layer and sealed to the substrate along with a peripheral seal. In this embodiment, the laminated seal 52 of the present invention is provided over the entire top electrode of the display, with a polymer layer 56 and an inorganic layer 54 over it.

FIG. 2 shows another embodiment of a portion of the sub-pixel structure of the thick film dielectric electroluminescent display 100, in which the laminated seal 152 is provided entirely over the blue light emitter 138 of the display. It has been. Further, in this embodiment, the electroluminescent display 100 includes a substrate 120, a cover plate 122, an electroluminescent display structure 124 between the two, and an electroluminescent display structure 124 from one or more air pollutants. For protection, there is an optional peripheral seal (not shown) between the substrate 120 and the cover plate 122. The peripheral seal extends and contacts the cover plate 122 and the substrate 120. Then, the entire gap between the cover plate 122 and the substrate 120 is filled. The peripheral seal does not contact the electroluminescent display 124. Substrate 120 has a bottom electrode 130 thereon, followed by a thick film dielectric layer 132, a dielectric smoothing layer 134, and an optional thin film dielectric layer 136 made of a material such as barium titanate over them. . These subpixel columns are provided with a blue emitter layer 138 over the thin film dielectric layer 136, with an upper thin film dielectric layer 140 thereon, and three subpixel columns 142, 144 and 146 disposed thereon. Facilitates application of voltage to cause the layer to emit light The thin film dielectric layer 140 separates the subpixel columns 142, 144, 146 from the light emitting layer 138. The subpixel column 142 has a green color conversion layer 148 directly on it. Similarly, the subpixel column 144 has a red color conversion layer 150 directly thereon. The subpixel column 146 corresponding to the blue subpixel does not have a color conversion layer. Instead, the laminate seal 152 is provided on the color conversion layers 148 and 150 and directly on the subpixel column 146. Laminate seal 152 includes an inorganic layer 154 over a polymer layer 156. Laminate seal 152 is shown to fill void 155 without a color conversion layer, thus filling this space. The space 157 provided above the laminated seal 152 can be filled with an optically clear non-reactive material, or alternatively, the laminated seal 152 is provided to fill the space 157. A cover plate 122 is placed over the substrate facing the deposited layer and sealed to the substrate along with a peripheral seal.

FIG. 3 illustrates another embodiment of a portion of a sub-pixel of a thick film dielectric layer electroluminescent display 200, in which the display includes the lower polymer layer incorporating color conversion layers 248 and 250 of the present invention. A laminated seal 252 is provided. Further, in this embodiment, the electroluminescent display 200 includes a substrate 220, a cover plate 222, an electroluminescent display structure 224 between the two, and an electroluminescent display structure 224 from one or more air pollutants. An optional peripheral seal (not shown) is provided between the substrate 220 and the cover plate 222 for protection. The peripheral seal extends and contacts the cover plate 222 and the substrate 220. Then, the entire gap between the cover plate 222 and the substrate 220 is filled. The peripheral seal does not contact the electroluminescent display structure 224. Substrate 220 has a bottom electrode 230 thereon, followed by a thick film dielectric layer 232, a dielectric smooth layer 234, and an optional thin film dielectric layer 236 made of a material such as barium titanate over them. . An emissive layer 238 is provided over the thin film dielectric layer where the upper thin film dielectric layer 240 is shown in which the three subpixel columns 242, 244 and 246 are disposed. These subpixel columns facilitate application of a voltage for the light emitting layer to emit light. Thin film dielectric layer 240 separates subpixel columns 242, 244, 246 from light emitting layer 238. The subpixel column 242 has a green conversion layer 248 on it. Similarly, the subpixel column 244 has a red color conversion layer 250 thereon. The subpixel column 246 corresponding to the blue subpixel does not have a color conversion layer, but has a refractive index selected to minimize reflection of light between the layers, and on all subpixels in the next deposited inorganic layer. In order to give a smooth surface with an optically transparent part 255 of the lower polymer material. This part may be an optical blue filter or a space. A cover plate 222 is placed on the substrate facing the deposited layer and sealed to the substrate along with a peripheral seal.

In an embodiment of a process for manufacturing a sealed electroluminescent display of the present invention, a precursor material that is liquid or pasty with respect to the polymer layer of the sealing structure material in a contaminant-free atmosphere, such as a dry box Is down-processed. This is to avoid contamination of the getter material with water vapor that would cause the getter material to be deactivated (when the getter material is incorporated). In order to achieve a desired contaminant absorption capacity and contaminant absorption rate, the amount of getter material loaded into the seal material may be adjusted. Deposition and curing should also be done in a dry box to avoid water vapor contamination. In an embodiment of the inventive approach, the UV curable polymer layer is printed on top of the electrode array as a lacquer formation. Printing is performed by various methods including (but not limited to) indirect offset printing and roll coating. The polymer layer is then cured to have a smooth top surface to facilitate subsequent deposition of a smooth and substantially pinhole free thin film inorganic layer. A substantially pinhole free inorganic layer is vacuum deposited on the polymer layer.

Thick films as illustrated in WO 00/70917, 02/058438 and US Provisional Application 60/43439, the disclosures of which are hereby incorporated by reference in their entirety. Two test electroluminescent devices each comprising a dielectric layer and a blue emitting europium activated barium thioaluminate thin film emitting layer were constructed on a 5 cm square glass substrate. One device is a deposition by spin coating process, drying at 100 ° C. for 10 minutes, UV curing under an ultraviolet flux of 400 mJ / cm ² , and baking at 160 ° C. for 1 hour, Arch Chemical, Connecticut Sealed by a resin coating consisting of Fuji acrylic resin CT2000L manufactured by Norwalk, Connecticut. The other device was not covered with a polymer layer. The device without the polymer layer was operated in an ambient environment containing nitrogen at 5% relative humidity and the other device with the polymer layer was operated under ultra high purity nitrogen with a dew point of -78 ° C. The device was operated with an AC polarity voltage pulse with an amplitude voltage of 60 V exceeding the threshold voltage of the luminance onset for the device and a repetition rate of 240 Hz. FIG. 4 shows the relative luminous intensity as a function of operating time in these environments. As can be seen from the data, the device operated under ultra-high purity nitrogen showed much higher luminous intensity and a lower percentage of luminous intensity loss due to increased operating time. In addition, the test apparatus operated in an atmosphere of 5% relative humidity grew black spots over time, whereas the test apparatus operated under ultra high purity nitrogen did not. The data indicates that at least one of the polymer layer and / or the low humidity environment provides high brightness and stability.

[Example 2]
In this example, a test device similar to Example 1 was tested. One apparatus comprises a laminated seal structure of 1 μm thick polymer layer deposited by the method of Example 1 covered by 1 μm thick amorphous silicon nitride deposited by sputtering or low temperature chemical vapor deposition . The other device is the same as that of the first embodiment. The device with the laminated seal structure was operated using the same operation method as in Example 1 in an ambient environment at 22 ° C. and a relative humidity of 40%. Devices without a laminated seal structure were operated in a low humidity atmosphere at 22 ° C. and 5% relative humidity. FIG. 5 shows the light intensity according to the operating time of both devices. As can be seen from the data, the device with the seal structure including the silicon nitride layer has a high humidity and low brightness reduction rate even when the operating time is increased despite the high humidity operating environment. Holding. Furthermore, the test apparatus equipped with a seal structure including a silicon nitride layer did not grow black spots over time.

Claims (13)

An electroluminescent display,
A substrate;
A transparent cover plate;
A blue light-emitting addressable electroluminescent pixel array disposed between the substrate and the cover plate;
A photoluminescence color conversion layer that is arranged adjacent to the sub-pixels of the pixel array and converts blue light from at least some pixels in the pixel array into visible light of a different color, and is adhered to the color conversion layer A laminated seal comprising an optically transparent inorganic amorphous film layer, wherein the display is a thick film electroluminescent display;
The pixel array comprises: a lower electrode; a thick film dielectric layer; a smooth layer; a thin film dielectric layer; a light emitting layer; an upper thin film dielectric layer; display. The inorganic amorphous film layer is composed of silica, alumina, titania, indium oxide, tin oxide, indium tin oxide, tantalum oxide, zirconium oxide, chromium oxide, zinc oxide, aluminum nitride, silicon nitride, boron nitride, germanium nitride, chromium nitride. , Nickel nitride, boron carbide, tungsten carbide, silicon carbide, aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconium oxyboride, titanium oxyboride, silicon aluminum oxynitride (SiAlON), aluminum oxynitride (AlON), The display according to claim 1, wherein the display is selected from the group consisting of and combinations thereof.   The display according to claim 2, wherein the inorganic amorphous film layer is silicon nitride, silicon oxynitride, or a mixture thereof.   The display according to claim 1, wherein the inorganic amorphous film layer has a thickness of about 0.01 to 2 μm, or about 0.05 to 1 μm.   The color conversion layer includes a fluorescent pigment particle composition dispersed in an ultraviolet curable resin, and the pigment particle composition includes at least one die and a polymer material having an optional molecular additive. The display according to claim 1, wherein:   2. The peripheral seal of claim 1, further comprising a peripheral seal that contacts the substrate and extends from the substrate to the cover plate to prevent the electroluminescent display structure from being exposed to air pollutants. Display. An electroluminescent display,
A substrate ;
A blue light-emitting addressable electroluminescent pixel array;
An optically transparent laminated seal comprising a lower polymer layer deposited on and attached to the pixel array and an upper inorganic amorphous film layer deposited on the lower polymer layer;
A photoluminescence color conversion layer that adheres to the laminated seal and is arranged alongside the sub-pixels of the pixel array to convert blue light from at least some of the pixels in the pixel array into visible light of a different color;
A cover plate, in order, the display is a thick film electroluminescent display,
The pixel array includes: a lower electrode; a thick dielectric layer; a smoothing layer; a thin dielectric layer; a light emitting layer; an upper thin dielectric layer; and an upper electrode. Luminescent display.   8. The inorganic amorphous film layer is selected from the group consisting of silicon nitride, silicon carbide, silicon oxynitride, silicon aluminum oxynitride (SiAlON), aluminum oxynitride (AlON), and combinations thereof. Display as described in.   The display according to claim 7, wherein the inorganic amorphous film layer is silicon nitride or silicon oxynitride.   The display according to claim 7, wherein the inorganic amorphous film layer has a thickness of about 0.01 to 2 µm, or about 0.05 to 1 µm.   The color conversion layer includes a fluorescent pigment particle composition dispersed in an ultraviolet curable resin, and the pigment particle composition includes a polymer material having at least one die and an optional molecular additive. The display according to claim 7.   8. The display of claim 7, further comprising a peripheral seal extending from and contacting the cover plate to prevent the electroluminescent display structure from being exposed to air pollutants. A substrate;
A thick film dielectric electroluminescent display structure provided on the substrate;
Provided in the display, the laminated seal provided above the thick film dielectric electroluminescent display structure; turn provided with,
The laminated seal includes a lower polymer layer and an upper inorganic amorphous film layer deposited on the lower polymer layer, and the lower layer of the seal structure increases the pressure between the upper moisture-impermeable layer of the seal structure and the display structure. A hermetic electroluminescent display that provides a means to absorb or react with the evaporating vapor from the display structure to substantially prevent and avoid breakage of the upper moisture impermeable layer.